research papers

Ultra-small-angle neutron scattering with azimuthal

asymmetry
ISSN 1600-5767

X. Gua and D. F. R. Mildnerb*

Received 1 December 2015

Accepted 4 April 2016

Edited by G. Kostorz, ETH Zurich, Switzerland

Keywords: azimuthal asymmetric scattering;
double-crystal diffractometers; elliptic scattering
contours; slit-height smeared scattering; smallangle neutron scattering.

a
Department of Geosciences, Pennsylvania State University, University Park, PA 16802, USA, and bNIST Center for
Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA. *Correspondence
e-mail: david.mildner@nist.gov

Small-angle neutron scattering (SANS) measurements from thin sections of

rock samples such as shales demand as great a scattering vector range as possible
because the pores cover a wide range of sizes. The limitation of the scattering
vector range for pinhole SANS requires slit-smeared ultra-SANS (USANS)
measurements that need to be converted to pinhole geometry. The desmearing
algorithm is only successful for azimuthally symmetric data. Scattering from
samples cut parallel to the plane of bedding is symmetric, exhibiting circular
contours on a two-dimensional detector. Samples cut perpendicular to the
bedding show elliptically dependent contours with the long axis corresponding
to the normal to the bedding plane. A method is given for converting such
asymmetric data collected on a double-crystal diffractometer for concatenation
with the usual pinhole-geometry SANS data. The aspect ratio from the SANS
data is used to modify the slit-smeared USANS data to produce quasi-symmetric
contours. Rotation of the sample about the incident beam may result in
symmetric data but cannot extract the same information as obtained from
pinhole geometry.

1. Introduction
The typical range of scattering vectors measured on a pinhole
small-angle neutron scattering (SANS) instrument is 103 <
1, suitable for measuring correlations and dimenQ < 0.5 A
. The modulus of the scattering
sions in the range 101000 A
vector is defined by Q = (4/) sin (/2), or Q 2/ at small
angles, where  is the wavelength and  is the scattering angle,
and the measured dimensions are in the range of Q1. The
circular isointensity contours on an area detector for isotropic
systems that scatter with azimuthal symmetry may be
azimuthally averaged to obtain a one-dimensional plot of the
scattered intensity I(Q) as a function of Q. Moreover, a twodimensional detector enables observation of the intensity
from azimuthally asymmetric scattering samples. Efforts are
underway to extend the lower end of the Q range by a further
order of magnitude using pinhole geometry, in order to
examine dimensions as large as 1 mm (Brulet et al., 2008;
Dewhurst, 2014; Barker, 2015; Abbas et al., 2015).
For systems having dimensions greater than 1 mm, an
alternative method is required to extend the measurable range
to lower values of the scattering vector. Ultra-small-angle
neutron scattering (USANS) using a double-perfect-crystal
diffractometer can measure in the scattering vector range of
1 and examine dimensions in the range
105 < Q < 103 A
0.110 mm (Agamalian et al., 1997; Barker et al., 2005). This
instrumental arrangement is different in concept from pinhole
SANS in that it measures with high resolution in one direction
only, while having a much broader angular acceptance in the

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orthogonal direction in order to increase the count rate. This
has been made possible by improvements to the BonseHart
arrangement (Bonse & Hart, 1965) of silicon channel-cut
crystals by the elimination of the wings on the rocking curve
(Agamalian et al., 1997).
The smearing of the scattered intensity for USANS is
similar to slit-smeared small-angle X-ray scattering. If a model
that describes the scattering system exists, the smeared scattering function should be compared with the USANS data.
However, if such a model is unavailable, it is necessary to
desmear the USANS data in order to place the scattered
intensity I(Q) on an absolute basis with the SANS data from a
conventional pinhole instrument. The desmeared USANS
intensity from systems that scatter with azimuthal symmetry
may conveniently be concatenated with the azimuthally
averaged data obtained from the accompanying SANS
measurement. This procedure is not available for anisotropic
systems and consequently there are few USANS data
analyzed on azimuthally asymmetric systems. We examine the
analysis of systems for which the scattering pattern consists of
elliptical isointensity contours.
Asymmetric data often have contours with an elliptical
dependence, which indicate that the scattering is from entities
that have azimuthal symmetry about some unique axis within
the system (Summerfield & Mildner, 1983). Ciccariello et al.
(2000) have generalized the Porod law as a function of the
direction of Q for anisotropic samples. The unique axis may be
a stretched direction as in extruded materials (such as the
uniaxial drawing of polyethylene; Matsuba et al., 2013), or it
may be caused by uniaxial compaction as in geological samples
(Gu et al., 2015). Sector averages over a range of azimuthal
angles are taken so that the scattered intensity I(Q) is
obtained with reasonable statistics along the two orthogonal
directions.
The desmearing of USANS data for conversion to pinhole
geometry uses an iterative method (Lake, 1967) that is good
for symmetric scattering data but not for asymmetric scattering because the two orthogonal dimensions are not
commensurate. We investigate the information that might be
gleaned from USANS data collected from such anisotropic
systems by taking measurements from rock samples in
different orientations.

2. Geological samples
USANS measures the scattering of neutrons from scattering
length density (SLD) fluctuations in real space in the micrometre range. It is particularly useful for systems in materials
science and polymer science that are optically opaque and
therefore cannot be examined by light scattering. The technique is also useful for the study of porous media such as
cements. Here, we consider a geological example to probe the
difficulties of treating asymmetric scattering systems. [For a
review, see Radlinski (2006)]. We assume that we have a twophase system with scattering from pores within the rock,
arising from the difference in SLD of the pores relative to
some average SLD of the rock matrix.
J. Appl. Cryst. (2016). 49, 934943

The sample used in this study is a Dunkirk/Huron black

shale collected from an outcrop at Erie, Pennsylvania, USA.
The Dunkirk/Huron black shale is an important Devonianaged source rock and gas-producing reservoir in the Appalachian Basin (Milici & Swezey, 2006). The sample consists of
42.5 wt% quartz, 37 wt% illite, 8 wt% plagioclase, 6.5 wt%
chlorite and 6 wt% pyrite (determined by X-ray diffraction).
The total organic carbon (TOC) content is 8.33 wt% (determined by carbon combustion). The SLD of the rock matrix is
2, which is close to the typical
approximately 3.9  106 A
SLD of black shale (Gu et al., 2015, 2016) and much greater
than that of the empty pores (for which the SLD 0).
Differences in random composition within the rock lead to
additional background in the scattering data.
The pores in rocks and shales form a fractal microstructure
that gives rise to intense power-law scattering, so that there is
always multiple scattering present for geological samples.
Triolo et al. (2000) and Radlinski et al. (2000) have shown that
multiple scattering affects this dependence, causing deviation
from the power-law scattering resulting in incorrect analysis.
Even 1 mm thick samples are subject to strong multiple scattering. SANS measurements can benefit from having a shorter
wavelength, whereas the very small angles of USANS require
geological samples about 150 mm thick (Anovitz et al., 2009), a
reasonable compromise between an adequate scattered signal
and excessive multiple scattering.
We compare measurements when the scattering plane is
normal to the unique axis with those when the scattering plane
includes the unique axis. In the case of geological samples, the
unique axis is perpendicular to the plane of bedding.
Measurements have therefore been taken on thin sections of
rock that have been sectioned both parallel to and normal to
the bedding plane (see Fig. 1). We assume that both cuts are
representative of the particular rock system. Each sample was
fixed onto a quartz glass slide of thickness 1 mm with negligible scattering, which was itself attached to a gadolinium
aperture of diameter 12.7 or 6.35 mm, depending on the size of
the sample. Though these sections had a nominal thickness of
150 mm, micrometer measurements indicated that the cut
parallel to the bedding was 299 mm thick (within 10 mm), and
the cut perpendicular to the bedding was 238 mm thick.
The SANS measurements were performed on the pinhole
SANS instrument NG3 (Glinka et al., 1998) at the NIST
Center for Neutron Research (NCNR) in three different
configurations, with
/ 12% and sample-to-detector
neutrons, and of 13 m. The
distances of 1 and 4 m using 6 A
last configuration used MgF2 lenses in order to extend the
measurable range of the scattering vector (Choi et al., 2000)
, to enable Q = 1  103 A
1 to be
and a wavelength  = 8.09 A
reached for an overlap with the USANS range. Measurements
were taken on both the parallel- and perpendicular-cut
samples, and also with the perpendicular-cut sample rotated
continuously in the beam. Labeled in Fig. 1 are the three
principal directions of the sample, X and Y within the bedding
plane, and Z the normal to the plane. After background
subtraction using a clean quartz slide measurement, the data
for the parallel-cut sample were averaged azimuthally to
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produce I(Q). Sector averaging over azimuthal angles

30 is necessary for the perpendicular-cut measurement
(averaging using
15 with fewer pixels results in noisier
data).
Similar USANS measurements were performed on the
double-crystal instrument BT5 (Barker et al., 2005) at the
with
/ = 5.9%. The
NCNR using a wavelength  = 2.38 A
double-crystal arrangement has an instrumental (full width at
1 in the horizontal
half-maximum) resolution of 2  105 A
5
1, and
direction, with a Q range of 3  10 < Q < 3  103 A
with a relaxed resolution in the vertical y direction
1). Note that the perpendicular-cut sample was
( 0.117 A
first mounted with the bedding (direction Y) horizontal, in the
direction of the high-resolution USANS scan, and then
remounted so that the normal to the bedding (direction Z) was
in the Q scan direction. Both sets of measurements were
reduced to an absolute scale using the NIST data-reduction
procedure (Kline, 2006).

Scattering from the perpendicular-cut sample results in

elliptical isointensity contours. This signifies that the scattering
is from entities that have azimuthal symmetry about some
unique axis within the system. The assumption is that the rock
is a two-phase scattering system, with pores that are flattened
such that, on average, they are isotropic (randomly oriented)
within the plane of the bedding, with the normal to the
bedding as the unique axis. We also assume that the average
pore dimension in this direction is less than that within the
plane of bedding. Hence the scattering pattern for the
perpendicular-cut sample has an elliptical form of isointensity
contours, with the short axis corresponding to the Y direction
of the bedding plane and the long axis corresponding to Z, the
direction normal to the bedding.
Fig. 2 shows the azimuthally averaged SANS results, indicating the intensity as a function of Q over the range 0.001 <
1 after correction for background and transmission.
Q < 0.4 A
The measurement labeled X is the azimuthally averaged value
of the symmetric scattering for the sample cut in a plane
parallel to the bedding, i.e.

3. SANS results
Fig. 1 shows the two-dimensional SANS scattering patterns for
the samples cut parallel and perpendicular to the bedding
plane. We label the three principal directions, so that the
bedding plane is always the XY plane with the neutron beam
in the Z direction, and the perpendicular-cut sample defines
the YZ plane with the neutron beam in the X direction. The
two-dimensional SANS patterns are plots of I(Qx, Qy, 0) with
the neutron beam along Z, and I(0, Qy, Qz) with the neutron
beam along X.



IX Q IQ cos ; Q sin ; 0 0<<2 :

The perpendicular-cut measurement has elliptical isointensity

contours, with Y and Z referring to the 30 sector average
about the shorter axis and along the longer axis of the
contours, respectively, i.e.

Figure 1
A schematic diagram indicating the planes of the two cuts, one parallel
and the other perpendicular to the plane of bedding of the sample rock.
The unique axis is the normal to the bedding plane. For each orientation
of the sample, the scattered neutron beam results in a pattern on the twodimensional detector. The scattering has circular (azimuthally symmetric)
contours when the beam is incident along the Z direction on the sample
cut parallel to the bedding plane XY, and elliptical (azimuthally
asymmetric) contours when the beam is incident along the X direction
on the sample cut perpendicular to the bedding plane YZ.

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Gu and Mildner

Azimuthally asymmetric USANS

Figure 2
The azimuthally averaged SANS results, with intensity plotted as a
1. The X curve is from the
function of Q over the range 0.001 < Q < 0.4 A
azimuthal average for the parallel-cut sample, the Y and Z curves are for
sector averages in directions parallel and normal to the bedding for the
perpendicular-cut sample, respectively, and the R curve is for the rotation
of the perpendicular-cut sample. Note that the Y curve is coincident with
the X curve since they are equivalent.
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Table 1
1 with n =
The straight-line fits of the SANS data to a simple power law AQn over the scattering vector magnitude range 1  103 < Q < 2  102 A
m
3.33, together with the straight line fits of the smeared USANS data to a simple power law AQ over the scattering vector magnitude range 2  104 <
1 with m = 2.16.
Q < 2  103 A
SANS measurement

Prefactor A ( 105 cm1)

USANS measurement

Prefactor A ( 104 cm1)

X curve, parallel-cut sample

Y curve, short axis for perpendicular-cut sample
Z curve, long axis for perpendicular-cut sample
R curve, rotation

2.21 (2)
2.15 (3)
14.26 (9)
7.11 (5)

X curve, parallel-cut sample

Y curve, bedding plane horizontal
Z curve, bedding plane vertical
R curve, rotation

6.00 (5)
9.86 (7)
20.25 (16)
15.76 (8)



IY Q I 0; Q sin ; Q cos =12<=2<=12


IZ Q I 0; Q sin ; Q cos =12<<=12

where is the azimuthal angle defined relative to the Z

direction. Note that the short axis corresponds to the larger
dimension in real space and is therefore the Y direction which
is within the bedding plane. Consequently, the values for Y are
coincident with those for X.
We can perform straight-line fits to the loglog plot,
1, the
assuming that, over the range 0.001 < Q < 0.02 A
scattering intensity obeys a power law
IQ AQn ;

where A is a prefactor. Table 1 gives the results. We find that,

over this Q range, all the measurements can be fitted with the
same power-law exponent n = 3.33 (4).
We assume that the Q dependence of the scattering is
separable from the azimuthal dependence, so that we may
write the intensity as
h
1=2 in
IQ; A Qn a2 cos2 b2 sin2 Q ; 4
where is the azimuthal angle relative to the normal to the
bedding plane. This approximation is reasonable provided that
the Q dependence does not change over the Q range
considered. This allows the possibility of elliptically averaging
the data (Reynolds & Mildner, 1984).
Fig. 3 illustrates the anisotropy by showing the scattering
1 as a
intensity for the perpendicular-cut sample at Q = 0.02 A
function of azimuthal angle. In the = 0 (or Z) direction,
IZ(Q) = AZQn anQn, and in the = /2 (or Y) direction,

IY(Q) = AYQn bnQn. The factor a/b corresponds to the

ratio of the long ( = 0) and short ( = /2) semi-axes of the
isointensity contours. Also, since AZ/AY = (a/b)n, shifting the
values of the coordinate Q to (b/a)Q for the Z data allows all
three measurements to be made coincident. Alternatively,
Fig. 4 shows that the same result can be obtained by multiplying the intensity values for the Z plot by (b/a)n. (A similar
relationship will be used in the analysis of the smeared
USANS data.)
From the fitted parameters given in Table 1, we find the
value of AZ/AY = 6.3 (10) (all quoted uncertainties and error
bars are one standard deviation). Assuming n = 3.33 (4), this
indicates that the ratio a/b of the elliptical contours has a mean
value for a/b = (AZ/AY)1/n = 1.76 (2). In addition, Fig. 5 shows
the ratio of the long- to short-axis intensities as a function of Q
1 with a mean value of
in the range 1  103 < Q < 1  102 A
7.11 (14), indicating a mean value for a/b = 1.80 (2). These
results show that, on average, the pores have a larger
dimension within the plane of bedding and a shorter dimension in the direction normal to the bedding.
We have also performed a measurement with the sample
placed within a rotation device (Olsson et al., 2013) which was
originally designed to avoid sedimentation of colloidal particles. With the perpendicular-cut sample rotated uniformly
around the incident neutron beam, the scattering intensity is
an average over all azimuthal angles and is symmetric for
given values of the scattering vector Q, i.e.

Figure 3
1 as a function of azimuth when (a)
The scattered intensity at Q = 0.02 A
the sample is cut parallel to the bedding with scattering in the XY plane,
and (b) the sample is cut perpendicular to the bedding with scattering in
the YZ plane. This shows that the Y measurement ( = /2) has a
similar intensity to the X measurement. The YZ data are fitted to
equation (4) so that I() [cos2 + (a/b)2sin2]n/2, where a/b = 1.76 and
n = 3.33.
J. Appl. Cryst. (2016). 49, 934943

Figure 4
A schematic diagram showing intensity I versus Q for the Y and Z
measurements, indicating that the two curves can be made coincident
either (i) by multiplying the Q coordinate for the Z data by b/a or (ii) by
multiplying the Z intensity values by (b/a)n.
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IR Q I 0; Q sin ; Q cos 0<<2
D
n=2 E n
a2 cos2 b2 sin2
Q :

These data are given the designation R and the intensity

IR(Q) = ARQn cnQn, where
D
n=2 E
cn a2 cos2 b2 sin2
D
1=2 En
:
6
a2 cos2 b2 sin2
This generates an ellipse in polar coordinates, c2 = (a2cos2 +
b2sin2)1. The average of the azimuthal dependence is
therefore given by
1

hci =2 a E k;

sample. The figure also shows that the expected value for the
rotation measurement calculated from the Y and Z data
agrees well with the experimental results R.

4. USANS results
The double-perfect-crystal USANS instrument measures the
scattering for a given value of Q by summing the intensity in
the vertical direction within the divergence Qm of the incident beam of the instrument. That is, the smeared intensity
Ism,X(Q) for the parallel-cut sample is a line average given by
Ism;X Q 2Qm 1

IQ; q; 0 dq

Qm

where k = (1  b2/a2)1/2 is the eccentricity of the elliptical

contours, and E(k) is the complete elliptical integral of the
second kind (Abramowitz & Stegun, 1965; see also http://
keisan.casio.com). With a/b = 1.76 (2) obtained from the fit, k =
0.823 (5) and hci/a = 0.799 (3). Then AR = AZ (hci/a)n =
6.76 (11)  105 cm1, compared with the experimental value
of 7.11 (5)  105 cm1 from Table 1. Using the mean value
for a/b = 1.80 (2) obtained directly from the ratio of the
intensities in Fig. 5 gives AR = 6.61 (6)  105 cm1.
The scattering intensities have been determined at various
values of Q from the SANS data for each of the three data sets
for the perpendicular-cut sample. These values, normalized to
the intensity for the parallel-cut measurement, are shown in
Fig. 6, indicating that the Y data for the perpendicular-cut
sample are consistent with the X data for the parallel-cut

Q
Rm

2Qm 1

Q
Rm

I Q2 q2

1=2

dq;

Qm

where q is the vertical component and Q the horizontal

component of the scattering vector selected by the analyzer.
The desmearing procedure is valid only for azimuthally
symmetric scattering, and the smearing of the scattered
intensity makes the analysis of USANS data problematic for
asymmetric scattering.
Fig. 7 shows the transmission-corrected slit-smeared
USANS results as a function of Qx, the scattering vector in the
horizontal high-resolution direction. For these measurements
on the perpendicular-cut sample, Y designates that the
bedding plane of the sample is placed in the horizontal plane
of the instrument, resulting in elliptical contours on a twodimensional detector with the longer axis in the vertical

Figure 6
Figure 5
The ratio of the long- to short-axis intensities from the Z and Y curves,
1 with
plotted as a function of Q for the range 1  103 < Q < 1  102 A
a mean value 7.11 (14). Taking the exponent n = 3.33 (4), this indicates a
mean value for a/b = 1.80 (2).

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Azimuthally asymmetric USANS

Values of the SANS intensity at selected values of the scattering vector

for the three perpendicular-cut measurements, the short-axis Y curve, the
long-axis Z curve and the rotated-sample R curve, normalized to the
intensity of the parallel-cut X curve. Also shown is the intensity for the
rotation calculated from the Y and Z curves.
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direction. Similarly, Z designates that the bedding plane is
placed in the vertical plane of the instrument, with the longer
axis of the elliptical contours in the horizontal direction.
In Appendix A we compare isocontours for the two
orientations of the perpendicular-cut sample with those for the
parallel-cut sample in order to determine the expected relative
intensities of the smeared USANS curves. The integral over
the slit height is greater when the bedding plane is in the
instrument horizontal direction, the Y measurement, than for
the parallel-cut sample. This is what is observed in Fig. 7 for
the smeared data, where the Y curve is no longer coincident
with the X curve for the parallel measurement as was the case
with the corresponding SANS measurements. Similarly, we
find that the Z measurement with the bedding plane in the
instrument vertical direction is reduced relative to the longeraxis SANS measurement. In addition, the curve for the
perpendicular-cut sample rotated in the neutron beam also lies
between the two, but is now closer to the Z curve.
We compare the four smeared USANS measurements in
Fig. 7. We performed straight-line fits to the loglog plot,
1,
assuming that, over the range 2  104 < Q < 2  103 A
m
the data are given by a power law Is(Q) = AQ . The results
are given in Table 1. Again, we find that, over this Q range, all
the gradients are similar, with the exponent m = 2.16 (4). The
large ratio (>5000) of the vertical to horizontal divergences
means that the integral in equation (8) extends over a large
range of q for all values of Q. Consequently, a power-law
scattering such as Qn becomes slit smeared as Qm, where

m = n  1 for n > 2. We find that this relationship holds as

expected for the azimuthally symmetric measurements.
With the perpendicular-cut sample rotated uniformly
around the incident neutron beam, the scattered intensity is an
average of the smeared intensity over all azimuthal angles or
orientations of the sample for given values of the horizontal
component of the scattering vector. The rotation measurement is therefore given by
Ism;R Q 2Qm 1 21

R2
0

Q
Rm

I0; q; Q cos dq: 9

Qm

By analogy with equation (7) we obtain

Ism;R Q =21 Ism;Z Q E k;

10

where Ism,Z(Q) is the smeared intensity when the bedding

plane is in the vertical direction. Using the results given in
Table 1, we find AZ/AY = 2.05 (2). With the exponent m =
2.16 (4), we find a/b = 1.39 (2), a value much lower than that
determined from the SANS data. The value of k is 0.695 (10),
and hci/a = (/2)1E(k) = 0.865 (5). Then AR = AZ(hci/a)m =
14.80 (21)  105 cm1, which compares reasonably with the
experimental value of 15.76 (5)  105 cm1 from Table 1.
The curves deviate from a simple power law at the lower
values of scattering vector. Straight line fits to AQm over the
1 (a range much lower than
range 5  105 < Q < 2  104 A
in Table 1) give an average exponent m = 1.78 (9). The distinct
separation in intensity for all four USANS plots for Q >
1 becomes less evident at the lowest measured values
0.001 A
1 and the Z curve bends over more than
of Q 3  103 A

Figure 7
The slit-smeared USANS results plotted as a function of Qx, the
scattering vector in the horizontal high-resolution direction. The X curve
is for the parallel-cut sample, the Y and Z curves are for the
perpendicular-cut sample with the bedding plane in the horizontal and
vertical directions, respectively, and the R curve is for the rotation of the
perpendicular-cut sample.
J. Appl. Cryst. (2016). 49, 934943

Figure 8
The ratio of the smeared USANS intensities for the perpendicular-cut
sample with the bedding plane parallel and perpendicular to the
scattering plane, plotted as a function of Q for the range 4  105 <
1. The line is a hyperbolic fit to the data: IZ/IY = 2.31 (3)
Q < 2.5  103 A
 3.33 (26)  105/Q.
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the others. This might suggest that, at correlation distances
much greater than 10 mm, the pores within the rock tend on
average to become less anisotropic. This could also be an
artifact of measurement close to the incident beam, and
indeed some researchers (King et al., 2015) discount data
1 on account of multiple scattering
below Q = 1  104 A
caused by thicker samples than used here. Whatever the
reason, this does not contradict the fact that the smaller scale
pores are anisotropic, as shown by the SANS results.
The separation of the Q dependence from the azimuthal
dependence can also be extended to the USANS data. Fig. 8
shows the ratio IZ/IY of the smeared intensity values for the
perpendicular-cut sample with the bedding plane parallel and
perpendicular to the scattering plane as a function of Q for the
1. Clearly the model has
range 4  105 < Q < 2.5  103 A
broken down, but this might be expected since the ratio a/b
must approach unity as the porosity becomes less anisotropic
at values of Q well beyond the SANS range, corresponding to
very large distances. The plot indicates that the ratio is a
hyperbola that may be fitted to IZ/IY = C  Q0/Q, where C =
1. This suggests that
2.31 (3) and Q0 = 3.33 (26)  105 A
there is little evidence of loss of anisotropy in the pores within
this sample for a correlation distance at least of the order of
2/Q0 20 mm.

5. Desmearing USANS data

We have desmeared the X and R data; the inversion procedure assumes knowledge of the smeared intensity over the
entire range of Q, so the data are extrapolated to large Q to
minimize truncation problems. We have performed straight-

line fits to the loglog plot, assuming that, over the range 2 
1, the data are given by a power law
104 < Q < 2  103 A
n
I(Q) = AQ . Again we find that, over this Q range, the
gradients are similar, with the exponent n = 3.15 (7). This is
close to the value of n = 3.33 (4) obtained for the SANS data
(see Table 1). Though it is not strictly valid we have also
desmeared the Y and Z data.
Fig. 9(a) shows all four of the desmeared USANS results on
the same plot as the SANS results. In the region around Q =
1 where the SANS and USANS data meet, there is a
0.001 A
smooth transition in scattering intensity for the symmetric
parallel-cut case X, and also for the rotation case R for the
perpendicular-cut sample which is quasi-symmetric. The
desmearing algorithm correctly produces a curve for the
azimuthally symmetric case that concatenates well with the
SANS results. On the other hand, we observe a shift in the
scattering intensity for both of the asymmetric perpendicularcut measurements. These abrupt changes in the combined data
can be better observed in Fig. 10(a), which shows the scattering intensity in the vicinity of the transition for both the Y
1.
and Z data at Q 0.001 A
We account for these changes in intensity at the crossover
point as follows. The desmearing algorithm requires that the
measured data be azimuthally symmetric, so that the scales of
Q in the horizontal scan axis and vertical integration axis are
commensurate, and the line averages are across the circular
contours. This procedure determines a smooth transition from
the SANS curve to the desmeared USANS result. The Y
SANS curve is from a sector average at the lowest intensity of
the two-dimensional data, whereas the Y USANS intensities
are derived from line averages in the integration direction

Figure 9
The combined results from the desmeared USANS (open square symbols) and the SANS (filled square symbols) measurements (a) before and (b) after
modification to the USANS data. The parallel-cut (brown X curve) and the rotational (green R curve) measurements show a smooth transition, whereas
for the perpendicular-cuts before modification the Y blue curve (with the bedding plane horizontal) has an upward jump at the transition and the Z red
curve (with the bedding plane vertical) has a downward jump. After modification, the transitions are no longer so abrupt.

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Figure 10
More detailed results from Fig. 9 in the vicinity of the overlap region of the SANS/USANS transition, showing (a) the upward jump for the Y curve and
the downward jump for the Z curve before modification, and (b) the less abrupt transition after modification. The SANS data have filled square symbols
and the USANS data have open square symbols. The line indicates the power law AQn for the X and Y curves, where n = 3.33.

over contours more widely spaced than in the scan direction,

resulting in an apparent greater intensity. Hence at the join of
the two data sets there is a positive shift in intensity from one
curve to the other. On the other hand, the Z SANS result is
from a sector average at the highest intensity of the twodimensional data. The Z USANS measurement is from a line
average over contours more closely spaced than in the scan
direction, resulting in an apparent lower intensity and a
downward shift in the curve.
We have found a method by which the USANS data for the
asymmetric scattering may be corrected for this desmearing
distortion. The SANS data for the two cases are used to
modify the USANS data for concatenation with the corresponding SANS data. The intensities Y and Z are multiplied
by the appropriate factor such that the values for the horizontal and vertical components of Q are commensurate, the
requirement for the desmearing algorithm. This procedure
forces the spacing of the elliptical contours in each direction to
become similar such that reciprocal-space steps in the integration axis have the same magnitude as those in the scan axis.
An elliptical contour has a corresponding circular contour
of radius r = (ab)1/2, the geometric average of the two semiaxes of the elliptical contour. The ratio of the Z and Y
prefactors for the SANS measurements shown in Table 1 gives
the ratio a/b = 1.76 (2). For the Y measurement b/r = 0.75 (3),
and for the Z measurement a/r = 1.33 (3). Artificially multiplying the Y intensity data by a factor (b/r)m = 0.54 (5) and
then performing the desmearing operation results in modified
Y USANS data that concatenate with the Y SANS data and
are consistent with the X USANS data. Similarly, multiplying
the Z intensity data by a factor (a/r)m = 1.84 (6) and then
performing the desmearing operation results in modified Z
J. Appl. Cryst. (2016). 49, 934943

USANS data that concatenate well with the Z SANS data.

These results can be observed in Figs. 9(b) and 10(b). We have
found similar results using other shale samples.
This procedure results in an intensity for asymmetric scattering that is consistent over the wide Q range offered by
combined SANS and USANS. It requires the data themselves
to correct for the line averaging over non-circular contours,
with the aspect ratio a/b obtained from the SANS data.
Confidence in this analysis can be obtained by considering the
prefactors from the smeared USANS measurements given in
Table 1. The ratio AX/AY = 0.609 (7) gives a value of b/r =
(AX/AY)1/m = 0.79 (2), a value similar to that of 0.75 (3)
obtained above from the AZ/AY SANS measurements.
Moreover, the ratio of the modified USANS intensities for the
Z and Y curves may be determined from the unmodified ratio
shown in Fig. 8 by
AZ a=rm AZ am

2:05  1:762:16 :
11
AY b=rm AY b
This gives a value of 6.95 (24) for the intensity ratio, compared
with a value of 7.11 (14) for SANS shown in Fig. 5.
Note that modifying the intensity values by a given factor is
in effect the same as altering the sample thickness by the same
factor in the raw data correction. This begs a question
regarding the accuracy of the sample thicknesses. It affects
how well the data can be placed on an absolute basis, and
indicates the importance of the correct sample thickness.

6. Summary
We wish to modify USANS asymmetric data that follow a
power law such that they concatenate well with data collected
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using pinhole SANS. The ratio of the intensities for the Z and
Y SANS measurements depends on the aspect ratio a/b of the
elliptical scattering contours and on the power law exponent n:
AZ SANS an

:
12
b
AY SANS
The two measured smeared USANS intensities may each be
modified by the a/b ratio obtained from the SANS measurement to give
AZ USANS mod AZ USANS a=rm AZ USANS a=bm=2

13

AY USANS mod AY USANS b=rm AY USANS b=am=2 ;

14

and

so that
AZ USANS mod AZ USANS am

;
AY USANS mod AY USANS b

15

where m is the smeared USANS power-law exponent.

Ideally, if the power-law exponent were the same for both Q
ranges, we would find the modified USANS intensity ratio to
be the same as the SANS intensity ratio, i.e.
AZ USANS am an

;
16
b
AY USANS b

relative intensities of the various measurements have been

qualitatively explained.
Quantitative statements regarding USANS data are less
extractable because the desmearing algorithm is valid only for
azimuthally symmetric scattering. This might be overcome if
the elliptical contours were known to have the same aspect
ratio for all measurable values of the scattering vector. We
have developed a procedure that employs the ratio of the long
and short axes of the elliptical contours observed in the SANS
data. This result is used to modify the raw USANS intensity
data, producing quasi-symmetric data that can be desmeared
in the usual way. The final product is desmeared USANS data
that can be successfully concatenated with the corresponding
SANS data obtained in pinhole geometry.
A continuous rotation of the sample in the beam also
produces quasi-symmetric data that can be desmeared. It is
shown that this result agrees well with the results for the two
orthogonal orientations of the perpendicular-cut sample. The
reverse procedure i.e. deducing the ratio of pore sizes
parallel and perpendicular to the bedding from the rotational
measurement cannot be accomplished. We find that this
to 10 mm that
particular sample has pores in the range 30 A
have an aspect ratio of 1.7 (comparing dimensions in the
bedding plane with those normal to the bedding), whereas we
may consider the rock to be nearly isotropic for correlations
over distances much greater than 30 mm.

so that
AZ USANS anm

:
b
AY USANS

17

From Table 1 the SANS measurements give AZ/AY = 6.63 (10),

so that a/b = (AZ/AY)1/n = 1.77 (2). The value of n  m =
1.17 (6), so we might expect the USANS measurements to give
AZ/AY = 1.94 (7). For comparison, we find that the USANS
measurements from Table 1 give AZ/AY = 2.05 (2), so that a/b =
(AZ/AY)1/(n  m) = 1.85 (6).
Alternatively, Fig. 4 indicates that similar results may be
obtained by multiplying the variable Q by b/r = (b/a)1/2 for the
Y USANS data, and by a/r = (a/b)1/2 for the Z USANS data.

7. Conclusions
We have considered the analysis of the simplest form of
azimuthal asymmetric scattering for measurements at scattering vectors below the normal SANS regime using a doubleperfect-crystal USANS instrument. We would like to extract
useful quantitative information from the measured data, for
which no mathematical model of the scattering system is
available. We have taken scattering measurements from thin
shale rock samples that are known to have narrow pores that
are slit like. These samples have been cut both parallel and
perpendicular to the plane of bedding. The normal to the
bedding plane is the unique axis that determines that the
scattering contours for the perpendicular-cut samples are
elliptical. The slit-smeared USANS results for the paralleland perpendicular-cut samples in the two different orientations have been given as a function of scattering vector. The

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APPENDIX A
We assume that, over the range of measurements, the
angular dependence of the scattering can be separated from
the scattering vector dependence. The isointensity contours
corresponding to the arrangement with the scattering plane
normal to the bedding plane are elliptical in shape, given by
equation (4), where is the azimuthal angle relative to the Z
direction. That is, tan = Q/q, where Q and q are the horizontal and vertical components of the scattering vector,
respectively. Fig. 11 shows two contours of the same intensity.
The circular contour for the X measurement (with the
parallel-cut sample) is tangential at the point (Q0 , 0) with the
elliptical contour for the Y measurement, with the long axis in
the vertical direction and normal to the high-resolution scan.
Since a > b, IY(Q, q) > IX(Q, q) for all q. The smeared intensity
Ism(Q) at a value of Q is given by equation (8). Hence, the
relative smeared intensities are given by Ism,Y(Q, q) >
Ism,X(Q, q).
Desmearing the USANS asymmetric data results in an
upward shift in intensity observed in the Y direction for the
perpendicular-cut sample relative to the X direction. (For the
SANS pinhole measurements, the intensities in the Y direction
are coincident with the X direction, the symmetric scattering
case.) Similarly, there is a downward shift observed at the
crossover point for the perpendicular-cut sample in the
direction Z normal to the bedding plane. This is in contrast
with both the X and R curves which concatenate smoothly.
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Energy. This work utilized the NG3 SANS and BT5 USANS
instruments at the NCNR, which are supported in part by the
National Science Foundation under agreement No. DMR0944772. We thank Terry Engelder at Pennsylvania State
University for providing the shale samples. We also
acknowledge helpful discussions with John Barker.

References

Figure 11
A schematic diagram in reciprocal space indicating isointensity contours
of the same magnitude for the X (parallel-cut sample) measurement
(circular contour, shown in orange) and for the Y (perpendicular-cut
sample with the bedding plane horizontal) measurement (elliptical
contour, shown in blue). The contours are tangential at the point (Q0 , 0).
The path of the slit-smearing integral at constant Q is shown in green and
extends to Qm, corresponding to the maximum vertical divergence of
the incident beam. The intensity at (Q, q) is greater for the Y
measurement than for the X measurement for all Q, as is the integral
given by equation (8).

Fig. 11 shows that the ratio of the contour spacings in the

direction of the long axis is a/r, so that at (0, q), by analogy
with Fig. 4, IY/IX = (a/r)m, where r is the radius of the corresponding circular contour. In order to make the elliptical
contours commensurate for the desmearing algorithm, all
intensities for the Y USANS curve must be multiplied by a
factor (r/a)m = (b/r)m. Similarly, the intensities for the Z curve
should be multiplied by (a/r)m.

Acknowledgements
XG acknowledges support for the use of neutron scattering in
the analysis of rock porosity by the Department of Energy,
Basic Energy Sciences, grant No. DE-FG02-OSER15675 to
S. L. Brantley, and by the Laboratory Directed Research and
Development Program of Oak Ridge National Laboratory,
managed by UTBattelle LLC for the US Department of

J. Appl. Cryst. (2016). 49, 934943

Abbas, S., Desert, S., Brulet, A., Thevenot, V., Permingeat, P., Lavie,
P. & Jestin, J. (2015). J. Appl. Cryst. 48, 12421253.
Abramowitz, M. & Stegun, I. A. (1965). Handbook of Mathematical
Functions. Mineola, New York: Dover Publications.
Agamalian, M., Wignall, G. D. & Triolo, R. (1997). J. Appl. Cryst. 30,
345352.
Anovitz, L. M., Lynn, G. W., Cole, D. R., Rother, G., Allard, L. F.,
Hamilton, W. A., Porcar, L. & Kim, M.-H. (2009). Geochim.
Cosmochim. Acta, 73, 73037324.
Barker, J. G. (2015). Personal communication.
Barker, J. G., Glinka, C. J., Moyer, J. J., Kim, M. H., Drews, A. R. &
Agamalian, M. (2005). J. Appl. Cryst. 38, 10041011.
Bonse, U. & Hart, M. (1965). Appl. Phys. Lett. 7, 238240.
Brulet, A., Thevenot, V., Lairez, D., Lecommandoux, S., Agut, W.,
Armes, S. P., Du, J. & Desert, S. (2008). J. Appl. Cryst. 41, 161166.
Choi, S.-M., Barker, J. G., Glinka, C. J., Cheng, Y. T. & Gammel, P. L.
(2000). J. Appl. Cryst. 33, 793796.
Ciccariello, S., Schneider, J.-M., Schonfeld, B. & Kostorz, G. (2000).
Europhys. Lett. 50, 601607.
Dewhurst, C. D. (2014). J. Appl. Cryst. 47, 11801189.
Glinka, C. J., Barker, J. G., Hammouda, B., Krueger, S., Moyer, J. J. &
Orts, W. J. (1998). J. Appl. Cryst. 31, 430445.
Gu, X., Cole, D. R., Rother, G., Mildner, D. F. R. & Brantley, S. L.
(2015). Energy Fuels, 29, 12951308.
Gu, X., Mildner, D. F. R., Cole, D. R., Rother, G., Slingerland, R. &
Brantley, S. L. (2016). Energy Fuel. In the press.
King, H. E. Jr, Eberle, A. P. R., Walters, C. C., Kliewer, C. E., Ertas, D.
& Huynh, C. (2015). Energy Fuels, 29, 13751390.
Kline, S. R. (2006). J. Appl. Cryst. 39, 895900.
Lake, J. A. (1967). Acta Cryst. 23, 191194.
Matsuba, G., Ito, C., Zhao, Y., Inoue, R., Nishida, K. & Kanaya, T.
(2013). Polym. J. 45, 293299.
Milici, R. C. & Swezey, C. S. (2006). USGS Open-File Report 20061237.
Olsson, A., Hellsing, M. S. & Rennie, A. R. (2013). Meas. Sci.
Technol. 24, 105901.
Radlinski, A. P. (2006). Rev. Mineral. Geochem. 63, 363397.
Radlinski, A. P., Radlinska, E. Z., Agamalian, M., Wignall, G. D.,
Lindner, P. & Randl, O. G. (2000). J. Appl. Cryst. 33, 860862.
Reynolds, L. E. & Mildner, D. F. R. (1984). J. Appl. Cryst. 17, 411416.
Summerfield, G. C. & Mildner, D. F. R. (1983). J. Appl. Cryst. 16, 384
389.
Triolo, F., Triolo, A., Agamalian, M., Lin, J.-S., Heenan, R. K., Lucido,
G. & Triolo, R. (2000). J. Appl. Cryst. 33, 863866.

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